3-(5- or 3-Substituted-5- or 3-isoxazolyl)-1-allyl or alkyl-4-substituted-5-substituted or unsubstituted-2-imidazolidinones for controlling weeds

ABSTRACT

Disclosed are compounds such as 3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone; their control of weeds such as johnsongrass; the process of making them; and intermediates for making them, the compounds being represented by a Formula I: ##STR1## wherein A is ##STR2## where R is an alkyl of up to six carbon atoms; an alkenyl of up to five carbon atoms; an alkynyl of up to five carbon atoms; a cycloalkyl selected from the group consisting of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; a haloalkyl of up to six carbon atoms; --R 4  --O--R 5 , or --R 4  --S--R 5 , where R 4  is an alkylene of up to six carbon atoms and R 5  is an alkyl of up to six carbon atoms; ##STR3## where Z is nitro (NO 2 ), chloro (Cl), bromo (Br), fluoro (F), or R 5 , and n is 0, 1, 2, or 3; R 1  is an alkyl of up to three carbon atoms, or allyl; R 2  is hydroxy (OH), chloro (Cl) or bromo (Br); and R 3  is hydrogen (H), an alkyl of up to four carbon atoms, allyl, or hydroxy (OH).

This is a division of application Ser. No. 122,633, filed Feb. 19, 1980.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention pertains to 3-[5- or 3-(alkyl, alkenyl, alkynyl,cycloalkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, optionallysubstituted phenylalkyl, optionally substituted phenoxyalkyl)-3- or5-isoxazolyl]-1-alkyl or allyl, -4-hydroxy or halo, -5-alkyl, allyl,hydroxy, or unsubstituted 2-imidazolidinones, such as3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinoneor3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone;the intermediates for forming the compounds; the process for forming thecompounds; and the control of the weeds with the compounds.

SUMMARY OF THE INVENTION

Compounds graphically represented by Formula I: ##STR4## wherein A is##STR5## where R is an alkyl of up to six carbon atoms; an alkenyl of upto five carbon atoms; an alkynyl of up to five carbon atoms; acycloalkyl selected from the group consisting of cyclopropyl,cyclobutyl, cyclopentyl, and cyclohexyl; a haloalkyl of up to six carbonatoms; --R⁴ --O--R⁵ or --R⁴ --S--R⁵, where R⁴ is an alkylene of up tosix carbon atoms and R⁵ is an alkyl of up to six carbon atoms; ##STR6##where Z is nitro (NO₂), chloro (Cl), bromo (Br), fluoro (F), or R⁵, andn is 0, 1, 2, or 3; R¹ is an alkyl of up to three carbon atoms, orallyl; R² is hydroxy (OH), chloro (Cl) or bromo (Br); and R³ is hydrogen(H), an alkyl of up to four carbon atoms, allyl, or hydroxy (OH) areuseful herbicides. In particular, the compounds3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinoneand3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4,5-dihydroxy-2-imidazolidinoneare particularly effective herbicides against weeds, particularly atvery low rates of applications. The invention also concernsintermediates of Formula II described herein which are useful forforming the compounds, the processes for forming the compounds, and themethod of controlling the weeds with the compounds.

DETAILED DESCRIPTION OF THE INVENTION

The novel agriculturally useful compounds are graphically represented byFormula I: ##STR7## wherein A is ##STR8## where R is an alkyl of up tosix carbon atoms; an alkenyl of up to five carbon atoms; an alkynyl ofup to five carbon atoms; a cycloalkyl selected from the group consistingof cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; a haloalkyl ofup to six carbon atoms; --R⁴ --O--R⁵ or --R⁴ --S--R⁵, where R⁴ is analkylene of up to six carbon atoms and R⁵ is an alkyl of up to sixcarbon atoms; ##STR9## where Z is nitro (NO₂), chloro (Cl), bromo (Br),fluoro (F), or R⁵, and n is 0, 1, 2, or 3; R¹ is an alkyl of up to threecarbon atoms, or allyl; R² is hydroxy (OH), chloro (Cl) or bromo (Br);and R³ is hydrogen (H), an alkyl of up to four carbon atoms, allyl, orhydroxy (OH).

Examples of compounds represented by Formula I are:

A. Those in which A is ##STR10## 1. R¹ is allyl; a. R³ is allyl;

a.1. R is ##STR11## and R² is as defined herein.3-[3-(1-(4-chlorophenyl)-1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-phenylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-phenoxypropyl)5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-chloro-2-imidazolidinone;

3-[3-(1-(2,4-dichlorophenoxy)-1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone.

a.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-methyl-1-(1-methylethylthio)ethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-chloro-2-imidazolidinone.

a.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-ethoxy-1-methylbutyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone.

a.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl-4-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-chloromethyl-1-ethylethyl-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-chloro-2-imidazolidinone.

a.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-1,5-di-(2-propen-1-yl)-4-bromo-2-imidazolidinone.

a.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-[3-cyclohexyl-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-cyclopropyl-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-cyclopentyl-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-chloro-2-imidazolidinone.

a.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1-ethyl-1-methylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone.

a.8. R is tert-butyl, and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-chloro-2-imidazolidinone.

a.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-1,5-di-(2-propen-1-yl)-4-hydroxy-2-imidazolidinone.

b. R³ is an alkyl of up to four carbon atoms;

b.1. ##STR12## and R² is as defined herein.3-[3-(1-(3,4-dimethylphenyl)-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-ethyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-(2-chlorophenyl)-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-5-propyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4-chloro-5-ethyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-chloro-5-butyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclopropyl-5-isoxazolyl)-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-(3-cyclohexyl-5-isoxazolyl)-4-hydroxy-5-butyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-ethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.8. R is tert-butyl; and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-chloro-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone.

b.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4-hydroxy-5-methyl-1-(2-propen-1-yl)-2-imidazolidinone.

c. R³ is hydrogen (H);

c.1. R is ##STR13## and R² is as defined herein.3-[3-(1-phenoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-phenyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclohexyl-5-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(3-cyclopentyl-5-isoxazolyl)-4-chloro-1-(2-propen-1-yl)-2-imidazolidinone.

c.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-ethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.8. R is tert-butyl; and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethylethyl-5-isoxazolyl]-4-chloro-1-(2-propen-1-yl)-2-imidazolidinone.

c.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d. R³ is hydroxy (OH);

d.1. R is ##STR14## and R² is as defined herein.3-[3-(1-phenoxy-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-phenylethyl)-5-isoxazolyl-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-bromo-5-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclohexyl-5-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(3-cyclopropyl-5-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethypropyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.8. R is tert-butyl; and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-chloro-5-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

2. R¹ is an alkyl of up to three carbon atoms;

a R³ is allyl;

a.1. R is ##STR15## and R² is as defined herein.3-[3-(1-phenyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-[3-(1-phenoxyethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone.

a.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-ethyl-2-imidazolidinone.

a.3. R¹ is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone.

a.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-propyl-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-5-(2-propen-1-yl)-1-ethyl-2-imidazolidinone.

a.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclohexyl-5-isoxazolyl)-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-(3-cyclopropyl-5-isoxazolyl)-4-chloro-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone.

a.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-ethyl-2-imidazolidinone;

3-[3-(1-methylpropyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2imidazolidinone.

a.8. R is tert-butyl, and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-chloro-5-(2-propen-1-yl)-1-propyl-2-imidazolidinone.

a.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone;

3-[3-(1,2-dimethyl-1-propen-1-yl)-5-isoxazolyl]-4-hydroxy-5-(2-propen-1-yl)-1-methyl-2-imidazolidinone.

b. R³ is an alkyl of up to four carbon atoms;

b.1. R is ##STR16## and R² is as defined herein.3-[3-(1-(2,5-dichlorophenyl)-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-(2,4-dimethylphenoxy)-1-methylethyl)-5-isoxazolyl]-4-hydroxy-5-ethyl-1-methyl-2-imidazolidinone.

b.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-5-ethyl-1-methyl-2-imidazolidinone.

b.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclopropyl-5-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(3-cyclohexyl-5-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-ethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.8. R is tert-butyl, and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-5-ethyl-2-imidazolidinone.

b.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

c. R³ is hydrogen (H);

c.1. R is ##STR17## and R² is as defined herein.3-[3-(1-phenyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-(4-chlorophenoxy)-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone.

c.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclopropyl-5-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

c.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1,1-dimethylpropyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,2-dimethylbutyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.8. R is tert-butyl; and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-chloro-1-methyl-2-imidazolidinone.

c.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

d. R³ is hydroxy (OH);

d.1. R is ##STR18## and R² is as defined herein.3-[3-(1-phenyl-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-phenoxyethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[3-(1-methyl-1-methylthioethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylthioethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[3-(1-methoxy-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methoxyethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1-chloro-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-chloromethyl-1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(3-trifluoromethyl-5-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-chloro-5-hydroxy-1-methyl-2-imidazolidinone.

d.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(3-cyclohexyl-5-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(3-cyclopropyl-5-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[3-(1,1-dimethylpropyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.8. R is tert-butyl; and R² is as defined herein.

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-chloro-5-hydroxy-1-methyl-2-imidazolidinone.

d.9. R is an alkenyl or alkynyl of up to five carbon atoms; and R² is asdefined herein.

3-[3-(1,1-dimethyl-2-propyn-1-yl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethyl-2-propen-1-yl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

B. Those in which A is ##STR19## 1. R¹ is allyl; a. R³ is allyl;

a.1. R is ##STR20## and R² is as defined herein.3-[5-(1-phenyl-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-(2-chlorophenoxy)-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxy-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4-hydroxy-1,1-di-(2-propen-1-yl)-2-imidazolidinone.

a.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylpropyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4-chloro-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclobutyl-3-isoxazolyl)-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-(5-cyclohexyl-3-isoxazolyl)-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylbutyl)-3-isoxazolyl)-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl)-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.8. R is tert-butyl, and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-chloro-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

a.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4-hydroxy-1,5-di-(2-propen-1-yl)-2-imidazolidinone.

b. R³ is an alkyl of up to four carbon atoms;

b.1. R is ##STR21## and R² is defined herein.3-[5-(1-phenylpropyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone.

3-[5-(1-(2-chlorophenoxy)-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

b.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone;

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone.

b.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxy-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

b.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-propyl-2-imidazolidinone.

b.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

b.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclohexyl-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-(5-cyclopropyl-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

b.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methyl-1-ethylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone.

b.8. R is tert-butyl, and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

b.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-methyl-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-5-ethyl-2-imidazolidinone.

c. R³ is hydrogen (H);

c.1. R is ##STR22## and R² is as defined herein.3-[5-(1-(2-methylphenyl)-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-phenoxy-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methyl-1-methylthiopropyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methoxy-1-methylpropyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylbutyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-chloro-1-ethylpropyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1-(2-propen-1-yl)-2-imidazolidinone.

c.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclopropyl-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(5-cyclohexyl)-3-isoxazolyl)-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methyl-1-ethylethyl)-3-isoxazolyl]-4-hydroxy-1-(2propen-1-yl)-2-imidazolidinone.

c.8. R is tert-butyl, and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

c.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1yl)-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d. R³ is hydroxy (OH);

d.1. R is ##STR23## and R² is as defined herein.3-[5-(1-phenyl-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-phenoxy-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxy-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-5-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclohexyl-3-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-(5-cyclobutyl-3-isoxazolyl)-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,2-dimethylpropyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.8. R is tert-butyl; and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1yl)-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-chloro-5-hydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

d.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4,5-dihydroxy-1-(2-propen-1-yl)-2-imidazolidinone.

2. R¹ is an alkyl of up to three carbon atoms;

a. R³ is allyl;

a.1. R is ##STR24## and R² is as defined herein.3-[5-(1-phenylbutyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(2-phenoxy-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-ethyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2propen-1-yl)-2-imidazolidinone;

3[5-(1-methylthiopropyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxyethyl)-3-isoxazolyl)-4-hydroxy-1-propyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1-methoxy-1-ethylethyl)-3-isoxazolyl]-4-hydroxy-1-ethyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylpropyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(2-chloro-1-methylbutyl)-3-isoxazolyl]-4-hydroxy-1-propyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclopentyl-3-isoxazolyl)-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-(5-cyclopropyl-3-isoxazolyl)-4-hydroxy-1-propyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-(5-methyl-3-isoxazolyl)-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.8. R is tert-butyl, and R² is as defined herein.

3-[5-(-1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-chloro-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

a.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1yl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-(2-propen-1-yl)-2-imidazolidinone.

b. R³ is an alkyl of up to four carbon atoms;

b.1. R is ##STR25## and R² is as defined herein.3-[5-(1-phenoxypropyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[5-(2-phenyl-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-diethyl-2-imidazolidinone.

b.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-5-propyl-2-imidazolidinone;

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-ethyl-5-methyl-2-imidazolidinone.

b.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4-chloro-1,5-dimethyl-2-imidazolidinone;

3-[5-(1-methoxy-1-methylpropyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylbutyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.5. R is trifluoromethyl (--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1,5-dimethyl-2-imidazolidinone.

b.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclohexyl-3-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(5-cyclopentyl-3-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-ethylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.8. R is tert-butyl; and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

b.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1-ethyl-5-methyl-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

c. R³ is hydrogen (H);

c.1. R is ##STR26## and R² is as defined herein.3-[5-(1-phenylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(2-(2-chlorophenyl)-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-ethyl-2-imidazolidinone;

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4-hydroxy-1-ethyl-2-imidazolidinone;

3-[5-(1-methoxy-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.5. R is trifluoromethyl(--CF₃); and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-1-methyl-2-imidazolidinone.

c.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclohexyl-3-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

3-(5-cyclopropyl-3-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone.

c.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylpropyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

c.8. R is tert-butyl, and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-chloro-1-methyl-2-imidazolidinone.

c.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.

d. R³ is hydroxy (OH);

d.1. R is ##STR27## and R² is as defined herein.3-[5-(1-phenyl-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-phenoxy-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.2. R is --R⁴ --S--R⁵ ; and R² is as defined herein.

3-[5-(1-methyl-1-methylthioethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-methylthioethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.3. R is --R⁴ --O--R⁵ ; and R² is as defined herein.

3-[5-(1-methoxy-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-methoxyethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.4. R is a haloalkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-chloro-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-chloromethyl-1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl2-imidazolidinone.

d.5. R is trifluoromethyl; and R² is as defined herein.

3-(5-trifluoromethyl-3-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-chloro-5-hydroxy-1-methyl-2-imidazolidinone.

d.6. R is a cycloalkyl as defined herein; and R² is as defined herein.

3-(5-cyclohexyl-3-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(5-cyclopentyl-3-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.7. R is an alkyl of up to six carbon atoms; and R² is as definedherein.

3-[5-(1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylpropyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

d.8. R is tert-butyl; and R² is as defined herein.

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl-3-isoxazolyl]-4-chloro-1-methyl-5-hydroxy-2-imidazolidinone.

d.9. R is an alkenyl or an alkynyl of up to five carbon atoms; and R² isas defined herein.

3-[5-(1,1-dimethyl-2-propyn-1-yl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethyl-2-propen-1-yl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.

In the compounds described herein, some compounds are more preferredthan others for the uses described herein. Thus, in those compoundswhere R¹ is an alkyl, the order of preference is as follows: methyl ispreferred over the straight alkyls, which are preferred over thebranched alkyls. As to R, branched alkyls are preferred over thestraight alkyls, which are preferred over methyl. When R is acycloalkyl, the preferred order of preference is cyclohexyl, followed bycyclopentyl, cyclobutyl, and cyclopropyl. When R is a haloalkyl of up tosix carbon atoms, the most preferred haloalkyl is trifluoromethyl (CF₃),followed by the branched haloalkyls, preferably the halo for thehaloalkyl is chlorine (Cl), and generally the monochloronated haloalkylsare preferred. When R² is as described herein, it is preferred that R²be hydroxy and next preferred is chlorine and bromine. When R³ is asdescribed herein, it is preferred that it be hydrogen, followed byhydroxy (OH), methyl, an alkyl, and allyl.

Preferred compounds have R² as hydroxy (OH).

Highly preferred compounds have R² as hydroxy, and R³ as methyl,hydroxy, or hydrogen, with hydrogen being preferred.

Very highly preferred compounds have R² as hydroxy; R³ as methyl,hydroxy, or hydrogen, with hydrogen being preferred; and R¹ as methyl.

The preferred compounds, highly preferred compounds, and very highlypreferred compounds which have R as 1,1-dimethylethyl (t-butyl),1-methylethyl (isopropyl), or trifluoromethyl are especially preferred.

In general, of all the compounds described herein, it is preferred thatA be ##STR28##

Examples of the most preferred compounds described herein are given indescending order of preference:

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[5-(1-methylethyl)-3-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(5-trifluoromethyl-3-isoxazolyl)-4-hydroxyl-1,5-dimethyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone;

3-[3-(1-methylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-1-methyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4,5-dihydroxy-1-methyl-2-imidazolidinone;

3[3-(1,1-dimethylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-[3-(1-methylethyl)-5-isoxazolyl]-4-hydroxy-1,5-dimethyl-2-imidazolidinone;

3-(3-trifluoromethyl-5-isoxazolyl)-4-hydroxy-1,5-dimethyl-2-imidazolidinone.

SYNTHESIS OF THE COMPOUNDS 1. General Synthesis of Compounds of FormulaI where R² is hydroxy (OH) and R³ is not hydroxy (OH).

The synthesis of the compounds described herein, wherein R² is OH and R³is not OH, proceeds according to the general reactions 1, 2, and 3 shownbelow: ##STR29##

Preparation of the Isocyanate

Five to 10 grams of the appropriate 5-substituted-3-aminoisoxazole (IIa)or 3-substituted-5-aminoisoxazole (graphically represented by FormulasIIa and IIb respectively), wherein R is as defined herein, is reacted(reaction 1) by adding it to a solution of phosgene and HCl inethylacetate (or other suitable solvent) prepared by adding an excess ofgaseous HCl to 50-100 milliliters of solvent, saturating this solutionwith phosgene at room temperature, and then adding another 50-100milliliters of solvent. The mixture is allowed to react while stirringovernight at room temperature and is then purged with nitrogen or argonto remove the unreacted phosgene. In those cases where a solid wasobtained, the product (graphically represented by Formulas IIIa or IIIb,which is an isocyanate of the appropriately substituted isoxazole) wasisolated by filtration and dried. In cases where no solid product isevident, the reaction mixture may be topped under vacuum to give theproduct as a viscous oil or glass.

Note, the appropriate isoxazole of Formula II may be obtained fromcommercial sources or made by any of the methods known in the art.

Preparation of Acetal Ureas

The appropriate isocyanate of Formula IIIa or IIIb is reacted with anequivalent amount of substituted amino-substituted-acetaldehydedialkylacetal represented by Formula IV, where R¹ is as defined herein;R⁶ is like R³ but is not hydroxy, that is, R⁶ is hydrogen, an alkyl ofup to four carbon atoms, or allyl; and R⁷ is an alkoxy of up to sixcarbon atoms, but preferably methoxy, an alkylthio of up to six carbonatoms, or a moiety reactive with the hydrogen atom attached to thenitrogen atom nearest the ring whereby a cyclic structure of Formula Iforms under cyclization reactions. The compounds are heated to reflux(2-15 minutes) in an inert solvent such as ether, benzene, toluene, orethylacetate, etc., and the reaction proceeds as shown by reactionequation (2) so as to form the urea product graphically represented byFormula V, where A, R¹, R⁶, and R⁵ are as defined herein. Some productsmay be produced as crystals directly from solution, but others may beinduced by the addition of hexane. If no solid forms, the solvent isremoved by distillation, evaporation, or other technique to yield thecrude product as an oil or solid. The product represented by graphicFormula V may be purified chromatographically, by washing with ether orhexane, or recrystallized from hexane/benzene or from ether/benzene orfrom ether/chloroform/benzene solutions, or by other methods known inthe art.

Note: The appropriate alkylamino-substituted-acetaldehyde dimethylacetalrepresented by Formula IV may be obtained from commercial sources ormade by any of the methods known in the art. Further other acetals suchas ethyl may be used, but methyl is preferred.

Preparation of the Compounds of Formula Ia

The appropriate acetal urea of Formula V (approximately three to fourgrams) is added to 150-200 milliliters of water containing 1.5-2milliliters of concentrated hydrochloric acid. The mixture is stirredvigorously and heated to reflux and reaction proceeds as shown byreaction equation (3). The hydrolysis is monitored by thin layerchromatography (alumina-ethylacetate) until complete and the productforms. The product, represented by Formula Ia, where A, R¹ and R⁶ are asdefined herein, in some cases may be crystallized directly from thereaction mixture upon cooling. In other cases, the compounds of FormulaIa are extracted with chloroform and isolated by stripping the solventunder vacuum. Those compounds which solidify upon concentration arefurther purified. In some cases, the compounds may be used directly asobtained. In other cases, crystallization is induced by seeding an ethersolution with a related compound, and the crystals formed may be furtherpurified.

2. General synthesis of compounds of Formula I where R² and R³ are bothhydroxy (OH)

Compounds represented by Formula I where R² and R³ are both hydroxide,as represented by Formula Ib, where A and R¹ are as defined herein:##STR30## are synthesized according to reaction equations 4 and 5.##STR31##

Preparation of the Ureas Represented by Formula VII

The appropriate isoxazol amine represented by Formula IIa or IIb isreacted with the appropriate isocyanate of Formula VI where R¹ is asdefined herein, in an inert solvent, such as benzene, ether, or toluene,with a small amount of alkylamine catalyst such as triethylamine attemperatures from about 15° C. to the reflux temperature of the mixture(reaction 4). The urea of Formula VII is generally separated from thereaction mixture by any of the techniques known in the art.

Preparation of the 4,5-dihydroxy-substituted-imidazolidinone Representedby Formula Ib

The appropriate urea of Formula VII is reacted with a 40 percent aqueousglyoxal solution which has been adjusted to a pH of 7.0-8.0 with asuitable base such as aqueous sodium hydroxide at temperatures from 15°C. to 80° C., but preferably from 20° C. to 40° C., over a period offrom ten (10) hours to up to 132 hours. The product (a compound ofFormula Ib) is separated by any of the techniques known in the art.

3. General synthesis of the compounds of Formula I where R² is bromo(Br) or chloro (Cl)

Those compounds represented by Formula I in which R² is bromo or chloroare prepared from compounds represented by Formulas Ia and Ib byreaction with about 10 percent excess of a halogenating agent (forexample, thionyl chloride, phosphorus oxychloride, phosphoroustrichloride, or phosphorous pentachloride), optionally in the presenceof a diluent (e.g. benzene, toluene, methylene chloride, etc.), andoptionally in the presence of an acid binding agent (such as an organicbase, alkali metal hydroxide, or carbonate), but preferably, without theaddition of an acid binder; and the acid formed is removed byconcentration, hydrolysis, or distillation. When compounds representedby Formula Ib are used, it is necessary to protect the hydroxy at the R³position by any of the known techniques used in synthesis reactions,such as alkylation, followed by removal of the alkyl group.

The following examples illustrate the synthesis of the compoundsdescribed herein.

EXAMPLE I Synthesis of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinonea. Formation of 5-(1,1-dimethylethyl)isoxazol-3-yl isocyanate

A 300 milliliter, 3-neck flask equipped with a magnetic stirrer,thermometer, and dry ice condenser/drying tube was charged with 100milliliters of ethylacetate solution containing 4.8 grams (0.034 mole)of 3-amino-5-(1,1-dimethylethyl)isoxazole. Anhydrous hydrochloric acidgas (10.0 grams) was bubbled into the solution, and then 20 grams ofphosgene was bubbled into the solution, which was cooled in an ice bath.The solution was allowed to stand at ambient temperature for 17 hoursand then the flask was purged with argon until no COCl₂ was detected.The solution was filtered under nitrogen, and the precipitate was washedwith benzene to give a precipitate containing about 0.034 mole (5.6grams) of 5-(1,1-dimethylethyl)isoxazol-3-yl isocyanate.

b. Formation of3-[5-(1,1-dimethylethyl-3-isoxazolyl]-1-methyl-1-(2,2-dimethoxyethyl)urea

At ambient temperatures, 4.2 grams (0.035 mole) ofmethylaminoacetaldehyde dimethylacetal in 15 milliliters of benzene wasrapidly added to 50 milliliters of benzene solution containing 0.034mole (5.6 grams) of the precipitate of5-(1,1-dimethylethyl)isoxazolyl-3-yl isocyanate (prepared above). Theresulting slurry was heated to reflux for two (2) minutes, filtered,cooled, and 20 milliliters of hexane added, but no crystals formed uponstanding and cooling in a refrigerator. It was then topped on a roto-vacat 70° C. to yield 5.7 grams of a viscous oil containing3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-1-(2,2-dimethoxyethyl)urea.The oil crystallized on cooling, and the crystals were recrystallizedfrom ethyl ether/hexane solution with refrigeration. The crystals wereremoved by suction filtration and air dried to yield 5.2 grams of whitecrystals of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-1-(2,2-dimethoxyethyl)urea.M.P. 80°-84° C., IR spectra (mull.) bands at 3260, 1670, 1600, and 1530cm⁻¹, MS ion at m/e at 285.

NMR (CDCl₃) 9.11δ (singlet, 1H); 6.61δ (singlet, 1H); 4.52δ (triplet,1H); 3.42δ (singlet, 8H); 3.50δ (doublet, 8H); 3.13δ (singlet, 3H);1.30δ (singlet, 9H).

c. Synthesis of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone

A round bottom flask was charged with 2.6 grams of the3-[5-(1,1-dimethylethyl)-3-isoxazoly]-1-methyl-(2,2-dimethoxyethyl)urea(prepared above), 150 milliliters of water and 1.5 milliliters ofconcentrated hydrochloric acid (HCl). The resulting mixture was heateduntil one phase formed, and crystals coated out on the sides of theflask and cooled; and the scrapings of the crystals and the solutionwere filtered. The crystalline precipitate was washed twice withseparate portions of H₂ O, and then air dried to yield 1.9 grams ofwhite crystals of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone.M.P. 173°-177° C., IR spectra (mull.) bands at 3400, 3140, 1700, and1590 cm⁻¹.

NMR (CDCl₃): 6.64δ (singlet, 1H); 5.83δ (multiplet, 1H); 4.92δ (broadsinglet, 1H); 3.83-3.17δ (multiplet, 2H); 2.89δ (singlet, 3H); 1.30δ(singlet, 9H).

EXAMPLE II Synthesis of3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinonea. Formation of 1-[3-(1,1-dimethylethyl)-5-isoxazolyl]-3-methylurea

A 50 milliliter flask with a magnetic stirring bar was charged with 1.3grams (0.0093 mole) of 3-(1,1-dimethylethyl)-5-isoxazolamine and 25milliliters of benzene. To this was added 1.7 grams of methyl isocyanateand one (1) drop of triethylamine; and the mixture was allowed to standovernight, after which it was heated to reflux for 7.5 hours and thenallowed to stand at room temperature for two (2) days. Thin layerchromatography showed only partial reaction, so a trace of4-dimethylaminopyridine and several milliliters of methyl isocyanatewere added and the mixture heated at reflux for 4.5 hours. The mixturewas then concentrated on a rotary evaporator to give 2.6 grams of aviscous red brown oil. Chromatography on alumina with chloroform/ethylacetate monitored by TLC gave fractions containing a single component.These fractions were combined and evaporated to give 0.67 gram of a paleyellow solid of 1-[3-(1,1-dimethylethyl)-5-isoxazolyl]-3-methylurea,M.P. 188°-196° C., which showed a molecular ion at 197 in the massspectrum.

b. Formation of3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone

The 0.67 gram (0.0034 mole) of1-[3-(1,1-dimethylethyl)-5-isoxazolyl]-3-methylurea prepared above wasdissolved in 5 milliliters of ethanol. To this was added 1.5 grams of a40 percent aqueous glyoxal solution previously adjusted to pH 7 withdilute sodium hydroxide solution. After standing at room temperature for2.5 days, the mixture was topped on a rotary evaporator and the residuewas washed with water and extracted with chloroform. The organic extractwas dried over magnesium sulfate, filtered, and topped on a rotaryevaporator to give 0.9 gram of viscous residue. Chromatography onalumina with ethylacetate/ethanol gave fractions containing a singlecomponent (as monitored by thin layer chromatography). These fractionswere combined and concentrated on a rotary evaporator to give 0.16 gramof oily residue which partially crystallized on cooling.Recrystallization from ether gave 0.08 gram of white crystals of3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone,M.P. 153°-156° C., which had mass, infrared and NMR spectra consistentwith the desired product.

EXAMPLE III Synthesis of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinonea. Formation of 1-[5-(1,1-dimethylethyl)-3-isoxazolyl]-3-methylurea

A 50 milliliter flask with a magnetic stirring bar, addition funnel,thermometer and condenser/drying tube was charged with 3.0 grams (0.021mole) of 5-(1,1-dimethylethyl)-3-isoxazolamine, a few crystals of4-dimethylaminopyridine and 20 milliliters of benzene. The funnel wascharged with 2.3 grams (0.040 mole) of methyl isocyanate in 5milliliters of benzene, which was added dropwise over five (5) minutes.After standing overnight, the mass of crystals which formed was isolatedby filtration, washed with hexane, and air dried to give 3.0 grams ofwhite powder of 1-[5-(1,1-dimethylethyl)-3-isoxazolyl]-3-methylurea,M.P. 188°-189° C.

b. Formation of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone

To a solution of 2.0 grams (0.010 mole) of1-[5-(1,1-dimethylethyl)-3-isoxazolyl]-3-methylurea in 50 milliliters of95 percent ethanol was added 7.3 grams of a 40 percent aqueous glyoxalsolution which had been previously adjusted to pH 7 with dilute sodiumhydroxide solution. After standing at room temperature overnight, thesolution was topped on a rotary evaporator to give an oily residue whichwas extracted with two 20 milliliter portions of chloroform. The extractwas washed with saturated sodium chloride solution, filtered throughsilicone-treated paper, and concentrated on a rotary evaporator to give2.0 grams of oily residue. Crystallization from ether gave 0.4 grams ofwhite crystals of3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone,M.P. 153°-157° C., which had consistent mass, infrared and NMR spectra.

INTERMEDIATE COMPOUNDS

The compounds represented by Formula V possess some herbicidalproperties, but in addition, are very useful because they are theintermediates for the synthesis of the novel compounds represented byFormula I.

APPLICATIONS OF THE COMPOSITIONS AGAINST WEEDS

The novel compounds of Formula I are particularly valuable for weedcontrol because they are toxic to many species and groups of weeds andare relatively nontoxic to many beneficial plants. The exact amount ofone or more of the compounds required depends upon a variety of factors,including the hardiness of the particular weed species, the weather, thetype of soil, the method of application, the kind of beneficial plantsin the same area, and the like. Thus, while the application of up toonly about one or two ounces of active compound per acre may besufficient for good control of a light infestation of weeds growingunder adverse conditions, the application of 0.2 pounds to 10 pounds ormore of an active compound of Formula I per acre may be required forgood control of a dense infestation of hardy perennial weeds growingunder favorable conditions.

a. Examples of Weeds Which May Be Controlled by the Compounds DescribedHerein

Weeds are undesirable plants growing where they are not wanted, havingno economic value, and interfering with the production of cultivatedcrops, with the growing of ornamental plants, or with the welfare oflivestock. Weeds may be classified as broadleaf or grassy weeds, aclassification which includes many types of known weeds. It is believedthat the compositions set forth herein, when applied in a herbicidallyeffective amount may control field pennycress, ryegrass, goosegrass,chickweed, purslane, smartweed, knotweed, wild buckwheat, kochia, medic,corn cockle, ragweed, sow-thistle, croton, cuphia, dodder, fumitory,groundsel, hempnettle, knawel, spurge, spurry emex, jungle rice,pondweed, dogfennel, carpetweed, bedstraw, ducksalad, naiad, chestgrass,fall panicum, witchgrass, switchgrass, watergrass, teaweed, wild turnipand sprangletop; biennials such as wild carrot, matricaria, wild barley,campion, chamomile, burdock, mullein, roundleaved mallow, bull thistle,houndstongue, moth mullein, and purple start thistle; or perennials suchas white cockle, perennial ryegrass, quackgrass, Canada thistle,bindweed, Bermuda grass, sheep sorrel, curly dock, nutgrass, fieldchickweed, dandelion, campanula, field bindweed, Russian knapweed,mesquite, toadflax, yarrow, aster, gromwell, horsetail, ironweed,sesbania bulrush, cat-tail, winter-cress, horsenettle, nutsedge,milkweed and sicklepod.

However, the important weeds of the genera against which most of thecompounds of the invention, particularly the preferred compoundsdescribed herein, and particularly the most preferred compound, are mosteffective preemergence and/or postemergence at 2 pounds per acre are:Sida, Datura, Brassica, Sorghum, Sesbania, Ipomoea, Avena, Abutilon,Setaria, Echinochloa and Digitaria weed species against which thecompounds of the invention, particularly the most preferred compound,are most effective are: Sida spinosa (L) (teaweed), Datura stramonium(jimsonweed), Brassica kaber (wild mustard), Setaria glauca (L) (yellowfoxtail), Gossypium hirsutum (L) (cotton as a weed), Sorghum halepense(johnsongrass), Sesbania spp. (coffeeweed), Ipomoea purpurea (L) Roth(tall morningglory), Avena fatua (wild oats), Abutilon theophrasti (L)(velvetleaf), Echinochloa crusgalli (L), (barnyardgrass), and [Digitariasanguinalis (L) (crabgrass, large), preemergence].

The most preferred compound,3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone,is very effective against the above-mentioned genera and species ofweeds, as well as being safe to use on rice, when applied preemergenceat rates of up to 0.5 pound per acre. At preemergence rates as low as0.5 pound per acre, the compound3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinonestunts and slows the growth of Cyperus esculentus (L) (yellow nutsedge).

b. Description of the Method of Controlling Weeds

As used herein and in the Claims, the method of controlling the weedscomprises contacting the weeds with a herbicidally effective amount of acompound represented by the graphic formula described herein. The term"contacting the weeds" refers to any method of contacting the weeds,both preemergence (before the weeds appear) and/or postemergence (afterthe weeds appear), such as applying granules of the compound to the soilprior to emergence, or spraying a solution of the compound or compoundsdescribed by the general formula, or any other method known in the artby which the weeds are contacted either before they emerge or after theyemerge, or both before and after they emerge, with one or more of thecompounds represented by the general Formula I described herein. Thephrase "herbicidally effective amount" refers to that amount requiredunder the environmental conditions in order to effectively control, thatis, by which the weeds are injured so as not to be able to recover fromthe application of the compound, or to be killed by the compound.

c. General Application of the Compounds

For practical use as herbicides, the compounds of this invention aregenerally incorporated into herbicidal formulations which comprise aninert carrier and a herbicidally toxic amount of a compound mentionedherein. Such herbicidal formulations enable the active compound to beapplied conveniently to the site of the weed infestation in any desiredquantity. These formulations can be solids such as dusts, granules orwettable powders or they can be liquids such as solutions, aerosols oremulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the activecompound with a solid inert carrier such as the talcs, clays, silicas,prophyllite, and the like. Granular formulations can be prepared byimpregnating the compound, usually dissolved in a suitable solvent, ontoand into granulated carriers such as the attapulgites or thevermiculites, usually of a particle size range of from about 0.3 to 1.5millimeters. Wettable powders, which can be dispersed in water or oil toany desired concentration of the active compound, can be prepared byincorporating wetting agents into concentrated dust composition.

In some cases, the active compounds are sufficiently soluble in commonorganic solvents such as kerosene or xylene so that they can be useddirectly as solutions in these solvents. Frequently, solutions ofherbicides can be dispersed under superatmospheric pressure as aerosols.However, preferred liquid herbicidal formulations are emulsifiableconcentrates, which comprises an active compound according to thisinvention and as the inert carrier, a solvent and an emulsifier. Suchemulsifiable concentrates can be extended with water and/or oil to anydesired concentration of active compound for application as sprays tothe site of the weed infestation. The emulsifiers most commonly used inthese concentrates are nonionic or mixtures of nonionic with anionicsurface-active agents. With the use of some emulsifiers systems, aninverted emulsion (water in oil) can be prepared for direct applicationto weed infestations.

A typical herbicidal formulation according to this invention isillustrated by the following example, in which the quantities are inparts by weight.

EXAMPLE IV PREPARATION OF A DUST

    ______________________________________                                        Product of Example I                                                                             10                                                         Powdered Talc      90                                                         ______________________________________                                    

The above ingredients are mixed in a mechanical grinder-blender and areground until a homogeneous, freeflowing dust of the desired particlesize is obtained. This dust is suitable for direct application to thesite of the weed infestation.

d. Mixtures of Compounds Alone or in Mixtures

Although all of the compounds described herein and represented by thegeneral formula described herein are useful as herbicides, some of theseare preferred and are better for applications against weeds. In general,all of the compounds described herein may be used either alone ortogether in mixtures. When used in mixtures, the amount of ratio of onecompound to another may vary from 0.01 to 100.

e. Manner of Application of the Compounds of This Invention

The compounds of this invention can be applied as herbicides in anymanner recognized by the art. One method for the control of weedscomprises contacting the locus of said weeds with a herbicidalformulation comprised of an inert carrier and one or more of thecompounds of this invention as an essential active ingredient, in aquantity which is herbicidally toxic to said weeds. The concentration ofthe new compounds of this invention in the herbicidal formulations willvary greatly with the type of formulations will comprise from about 0.05to about 95 percent by weight of the active compounds of this invention.In a preferred embodiment of this invention, the herbicidal formulationscan also comprise other pesticides, such as insecticides, nematocides,fungicides, and the like; stabilizers, spreaders, deactivators,adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combinedwith other herbicides and/or defoliants, desiccants, growth inhibitors,and the like in the herbicidal formulations heretofore described. Theseother materials can comprise from about 5 percent to about 95 percent ofthe active ingredients in the herbicidal compositions. Use ofcombinations of the present invention provide herbicidal formulationswhich are more effective in controlling weeds and often provide resultsunattainable with separate formulations of the individual herbicides.

f. Examples of Other Pesticides and Herbicides for Combinations

The other herbicides, defoliants, desiccants and plant growthinhibitors, with which the compounds of this invention can be used inthe herbicidal formulations to control weeds, can include: chlorophenoxyherbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4-(2,4-DB), 2,4-DEB,4-CPB, 4-CPA, 5-CPP, 2,4,6-TES, 3,4-DA, silvex and the like; carbamateherbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and thelike; thiocarbamate and dithiocarbamate herbicides such as CDEC, metamsodium, EPTC, diallate, PEBC, pebulate, vernolate and the like;substituted urea herbicides such as norea, siduron, dichloroal urea,chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron,monolinuron, neburon, buturon, trimeturon, and the like; symmetricaltriazine herbicides such as simazine, chlorazine, desmetryne, norazine,ipazine, prometryn, atrazine, trietazine, simetone, prometone,propazine, ametryne, and the like; chloroacetamide herbicides such asalpha-chloro-N,N-dimethylacetamide, CDEA, CDAA,alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,4-(chloroacetyl)morpholine, 1-(chloroacetyl)piperidine, and the like;chlorinated aliphatic acid herbicides such as TCA, dalapon,2,3-dichloropropionic acid, 2,2-TPA, and the like; chlorinated benozicacid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA,dicamba, tricamba, ambien, fenac, PBA,2-methoxy-3,6-dichlorophenylacetic acid,3-methoxy-2,6-dichlorophenylacetic acid,2-methoxy-3,5,6-trichlorophenylacetic acid, 2,5-dichloro-3-nitrobenzoicacid, dual, metribuzin and the like; and such compounds asaminotriazole, maleic hydrazide, phenyl mercuric acetate, endothall,biuret, technical chlordane, dimethyl 2,3,5,6-tetrachlorotetraphthalate,diquat, erbon, DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin,trifluralin, solan, dicryl, merphos, DMPA, DSMA, MSMA, potassium azide,acrolein, benefin, bensulfide, AMS, bromacil,2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine-3,5-dione,bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone,diphenatril, DMTT, DNAP, EXD, ioxynil, isocil, potassium cyanate, MAA,MAMA, MCPES, MCPP, MH, molinate, NPA, paraquat, PCP, picloram, DPA, PCA,phrichlor sesone, terbacil, terbutol, TCBA, LASSO, planavin, sodiumtetraborate, calcium cyanamide, DEF, ethyl xanthogen disulfide, sindone,sindone B, propanil and the like. Such herbicides can also be used withthe compositions of this invention in the form of their salts, esters,amides and other derivatives whenever applicable to the particularparent compounds.

g. Examples of Herbicidal Control

The following examples illustrate the utility of the compositionsdescribed herein for the control of weeds.

These tests described herein were conducted in a laboratory underlaboratory conditions, using standard laboratory procedures.

EXAMPLE V

When the compound of3-[5-(1,1-dimethylethyl)-3-isoxazlyl]-1-methyl-4-hydroxy-2-imidazolidinone(Example I) was applied postemergence at two (2) pounds per acre to theweed species: Sida spinosa (teaweed), Sesbania spp. (coffeeweed),Gossypium hirsutum (L) (cotton as a weed), Setaria glauca (L) (yellowfoxtail), Abutilon theophrasti (L) (velvetleaf), Echinochloa crusgalli(L) (barnyardgrass), Avena fatua (L) (wild oats), Datura stramonium (L)(jimsonweed), Sorghum halepense (L) (johnsongrass), Ipomoea purpurea (L)Roth (morningglory, tall), and Brassica kaber (L) (wild mustard), at theend of twenty-one (21) days, many of the weeds were so severely injuredthat they could not recover, and others were killed.

EXAMPLE VI

When the compound3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-1-methyl-4-hydroxy-2-imidazolidinone(Example I) was applied preemergence at two (2) pounds per acre to theweed species: Sida spinosa (teaweed), Sesbania spp. (coffeeweed),Digitaria sanguinalis (L) (crabgrass, large), Setaria glauca (L) (yellowfoxtail), Abutilon theophrasti (L) (velvetleaf), Echinochloa crusgalli(L) (barnyardgrass), Avena fatua (L) (wild oats), Datura stramonium (L)(jimsnweed), Sorghum halepense (L) (johnsngrass), Ipomoea purpurea (L)Roth (morningglory, tall), and Brassica kaber (L) (wild mustard), all ofthe weeds were so severely injured that they could not recover, andothers were killed, at the end of twenty (20) days.

EXAMPLE VII

When the compound3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinoneof Example II was applied postemergence at one (1) pound per acreagainst the weed species: Sida spinosa (teaweed), Datura stramonium (L)(jimsonweed), Brassica kaber (L) (wild mustard), Setaria glauca (L)(yellow foxtail), Gossypium hirsutum (L) (cotton, as a weed), Sesbaniaspp. (coffeeweed), Abutilon theophrasti (L) (velvetleaf), Ipomoeapurpurea (L) Roth (moringglory, tall), and Avena fatua (L) (wild oats),at the end of twenty (20) days, most of the weeds were killed whileothers were so severely injured that they could not recover.

EXAMPLE VIII

When the compound3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone(Example II) was applied preemergence at one (1) pound per acre againstthe weed specia: Datura stramonium (L) (jimsonweed), Brassica kaber (L)(wild mustard), Setaria glauca (L) (yellow foxtail), Digitariasanguinalis (L) (crabgrass, large), Avena fatua (L) (wild oats), andEchinochloa crusgalli (L) (barnyardgrass), at the end of twenty (20)days, most of the weeds were killed, while others were so severelyinjured that they could not recover.

EXAMPLE IX

When the compound3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinoneof Example III was applied preemergence at one (1) pound per acreagainst the weed species: Sida spinosa (teaweed), Datura stramonium (L)(jimsonweed), Sesbania spp. (coffeeweed), Abutilon theophrast (L)(velvetleaf), Ipomoea purpurea (L) Roth (morningglory, tall), and Avenafatua (L) (wild oats), at the end of twenty (20) days, most of the weedswere so severely injured that they could not recover and some werekilled.

While the invention has been described with reference to the specificdetails of certain illustrative embodiments, it is not intended that itshall be limited thereby except insofar as such details appear in theaccompanying claims.

I claim:
 1. A method of controlling weeds which comprises contacting theweeds with a herbicidally effective amount of a compound of Formula I:##STR32## wherein: A is ##STR33## where R is an alkyl of up to sixcarbon atoms,an alkenyl of up to five carbon atoms, an alkynyl of of upto five carbon atoms, a cycloalkyl selected from the group consisting ofcyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, a haloalkyl of upto six carbon atoms, -R⁴ -O-R⁵ or -R⁴ -S-R⁵, where R⁴ is an alkylene ofup to six carbon atoms and R⁵ is an alkyl of up to six carbon atoms, or##STR34## where Z is nitro (NO₂), chloro (Cl), bromo (Br), fluoro (F),or R⁵, and n is 0, 1, 2, or 3; R¹ is an alkyl of up to three carbonatoms or allyl; R² is hydroxy (OH), chloro (Cl), or bromo (Br); and R³is hydrogen (H), an alkyl of up to four carbon atoms, allyl, or hydroxy(OH).
 2. The method as recited in claim 1, which is3-[3-(1,1-dimethylethyl)-5-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.3. The method as recited in claim 1, which is3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4,5-dihydroxy-1-methyl-2-imidazolidinone.4. The method as recited in claim 1, which is3-[5-(1,1-dimethylethyl)-3-isoxazolyl]-4-hydroxy-1-methyl-2-imidazolidinone.